In this work, a multilayered microcapsule is proposed and prepared for use in self-healing polymers. Reactants for atom transfer radical polymerization (ATRP) are separately introduced into different places of the microcapsule to construct a latent ATRP reactor. When a polymer containing these capsules is damaged, crack induced breakage of the tiny vessels would lead to contact of the aforesaid reactants and hence autonomous polymerization of the released monomer, so that the damaged portions are re-bonded. The formation of the microcapsules goes through four steps. Optimum synthetic conditions for each step are carefully explored. The experimental results indicate that the components included in the multilayered microcapsules maintain their room temperature reactivity within the time of interest. The single microcapsule-type microreactor is provided with broad applicability as it can work alone with no need for additional chemicals and can be tailor-made according to the requirements of different polymers to be repaired. (C) 2013 Elsevier Ltd. All rights reserved.